Propylene oligomerization process

ABSTRACT

A catalyst composition for the polymerization, including oligomerization and codimerization, of olefins is provided by combining (A) zirconium, (B) a monophosphine electron donor ligand, and (C) a Lewis acid-reducing agent, in molar ratios of (B) to (A) of about 1 to 10:1 and (C) to (A) of about 1 to 40:1. Preferred catalyst components are zirconium acetylacetonate, triphenylphosphine or tri-n-butylphosphine and ethylaluminum sesquichloride. The catalyst composition of this invention may be employed in the dimerization of olefins such as propylene as well as in codimerization reactions, such as the preparation of heptenes from propylene and butenes.

United States Patent [191 Motier et al.

[4 1 Dec. 17, 1974 PROPYLENE OLIGOMERIZATION PROCESS [73] Assignee: Atlantic Richfield Company, New

York, NY.

22 Filed: Apr. 29, 1969 21 Appl. No.: 820,302

[52] U.S. Cl 260/683.15 D, 252/431 P [51] Int. Cl. C07C 3/10 [58] Field Of Search 260/683.15 D; 252/431 P [56] References Cited UNITED STATES PATENTS 2,951,066 8/1960 Coover et al. 260/937 3,051,692 8/1962 Lyons 3,081,287 3/1963 Coover et al. 260/937 3,379,706 4/1968 Wilke 260/683.15 X

Nowlin et al. 252/437 X Bearden et a1 260/683.15

Primary ExaminerPaul M. Coughlan, Jr.

[57] ABSTRACT A catalyst composition for the polymerization, including oligomerization and codimerization, of olefins is provided by combining (A) zirconium, (B) a monophosphine electron donor ligand, and (C) a Lewis acid-reducing agent, in molar ratios of (B) to (A) of about 1 to 10:1 and (C) to (A) of about 1 to 40:1. Preferred catalyst components are zirconium acetylacetonate, triphenylphosphine or tri-n-butylphosphine and ethylaluminum sesquichloride. The catalyst composition of this invention may be employed in the dimerization of olefins such as propylene as well as in codimerization reactions, such as the preparation of heptenes from propylene and butenes.

. 2 Claims, N0 Drawings PROPYLENE OLIGOMERIZATION PROCESS This invention relates to a catalyst composition and its use in the polymerization, including codimerization and oligomerization, of olefins. In particular aspects, the invention relates to a process for the formation of hexenes by dimerization of propylene and to a catalyst therefor. In addition, the catalyst of this invention may be employed in codimerization reactions, such as the preparation of heptenes from propylene and butenes. The catalyst may be unsupported or carried by a suitable base.

Numerous catalysts have been disclosed in the prior art as suitable for the preparation of polymeric products of olefins, particularly to form low molecular weight dimers, trimers, tetramers, etc. of such olefins. Normally gaseous olefins such as propylene have, for example, been effectively dimerized using these catalyst systems to produce hexene fractions of varying compositions. The polymeric and oligomeric products produced in such reactions are often valuable in either the petrochemical field or the fuel industry or both. One of the major fractions of dimeric propylenes, 2- methylpentenes, can be utilized, for instance, for the synthesis of isoprene. Another propylene dimerization product, 2,3-dimethylbutene, is useful as a feed for the production of 2,3-dimethylbutadiene which in turn can be used in a multi-step synthesis of pyromellitic anhydride, or can be hydrogenated to yield 2,3- dimethylbutane, useful as an octane-enhancing ingredient in gasoline. The latter compound, for example, has the highest research octane number (103.5) of those paraffins having boiling points up to 140F.

It has now been found that complexes of zirconium with an organomonophosphine electron donor ligand, when combined with a non-protonic Lewis acid capable of forming a coordination bond with zirconium, and a reducing agent capable of reducing zirconium acetylacetonate to an oxidation state of less than 4 and even to 0, provide a catalyst composition having highly desirable physical and chemical characteristics and, particularly, excellent catalytic activity and selectivity for the polymerization, including codimerization and oligomerization, of low molecular weight olefins. To obtain such compositions, the catalyst-forming reactants can be combined in a molar ratio of electron donor ligand to zirconium of about 1 to 10:1, preferably about 2 to 7:1; and a Lewis acid-reducing agent to zirconium molar ratio of about 1 to 40:1, preferably about 10 to 20:1.

In the preparation of the catalyst composition of the present invention, the zirconium source is provided by compounds of the metal which are at least slightly soluble in some solvent wherein the zirconium-phosphine ligand complex can be formed. Preferred are the weak field ligand complexes, the ligands of which readily serve in solution as transfer agents. Suitable sources of the zirconium can include, for example, halides, e.g., ZrCh, ZrBm, Z114; zirconium sulfate; alkoxy derivatives, i.e., Zr(OR),, where R represents alkyl, aryl, aralkyl, and the like groups; alkoxy zirconium carboxylate, i.e., (R), ZrOOCR where R and R are as defined above as R; phosphine complexes, e.g., Zr:(C H)2 PC2H4P(C H5)2]X4, Where X is a Also available as zirconium sources are chelates formed by the zirconium and weak field ligands, such as B-diketones or ,B-ketocarboxylic acid esters and salts of carboxylic acids. Examples of these types of zirconium sources include B-diketonato zirconium (IV), acetylacetonato zirconium (IV), propylacetonato zirconium (IV), benzoylacetonato zirconium; chelates from B-ketocarboxylic acid esters; salts of saturated monocarboxylic acids, e.g., zirconium formate, zirconium propionate, and the like; salts of corresponding unsaturated monocarboxylic acids, e.g., zirconium acrylate, zirconium vinyl acetate and the like; salts of saturated dicarboxylic acids, e.g., zirconium adipate and the like; salts of corresponding unsaturated dicarbox ylic acids, e.g., zirconium muconate and the like; salts of cyclic and aromatic carboxylic acids, e.g., zirconium cyclohexane carboxylate, zirconium phenyl acetate, zirconium benzoate, zirconium phthalates, and the like; and alkoxycarboxylates, e.g., zirconium methoxyacetate and the like. Preferred as a source of zirconium is zirconium acetylacetonate.

The electron donor ligand component employed in preparing the zirconium complex component of the catalyst of the present invention is preferably a triorganophosphine corresponding to the general formula R 1 wherein R is a hydrocarbon radical, e.g., alkyl, aryl, alkaryl, aralkyl and cycloalkyl of from 1 to about 20 carbon atoms, preferably 2 to about 6 carbon atoms, and preferably devoid of olefinic or acetylenic unsaturation; different R groups may, of course, be present in the same phosphine molecule. When the phosphine component contains aromatic groups it is generally preferred that these have mono-cyclic structures, e.g., that the groups be selected from phenyl, alkylphenyl, or phenylalkyl radicals.

The presence of the electron donor ligand component, preferably a triorganophosphine, which apparently can enter into a complex-forming reaction with the zirconium compound, makes for a more active catalyst composition. The phosphine component is monodentate or unidentate, i.e., unifunctional, as regards the phosphorus atom. Use of multifunctional phosphines such as his (diphenylphosphino) ethane in place of the unidentate phosphine in the catalyst composition of the present invention has been found, for example, to result in a composition showing no catalytic activity for the dimerization of propylene. Examples of suitable phosphines for the composition of the present invention are triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-n-butylphosphine, tri-ndecylphosphine, tribenzylphosphine, tri-(4-nbutylphenyl) phosphine, and the like. The selection of a particular triorganophosphine may depend upon the polymerization product desired. In the preparation of hexenes by the dimerization of propylene, for example, use of tri-n-butylphosphinenormally produces a maximum of dimethylbutenes. Such products would be particularly desired if the hexene fraction were to be used in gasoline, since 2,3-dimethylbutenes possess high octane numbers.

The Lewis acid and the reducing agent functions of our catalyst are preferably supplied in a single compound. As examples of such compounds, there may be mentioned the acidic metal halides which correspond to the general formula:

wherein M is a metallic element of coordination number n whose halides are Lewis acids, X is a halogen having an atomic number of 9 to 53, i.e., fluorine, chlorine, bromine, iodine, R is hydrocarbyl, e.g., alkyl, of 2 to about 6 carbon atoms and y is a number having a value from greater than to n. Preferred metallic elements in the above compound include aluminum, magnesium, beryllium, lead, zinc and tin. Examples of suitable such acidic metal halides include alkylaluminum halides including mono-, sesqui-, and dihalides, aluminum trichloride, zinc chloride and stannic chloride. Specific examples of suitable alkylaluminum halides are diethylaluminum chloride, fluoride, iodide, and bromide; ethylaluminum dichloride, ethylaluminum sesquichloride, etc.

Where the particular reducing agent employed in the composition does not also perform as a Lewis acid, it is necessary to separately supply the Lewis acid to the catalyst composition. Examples of reducing agents which are suitable in the preparation of the catalyst composition but which do not perform as Lewis acids therein include trialkylaluminum, monoalkoxydialkylaluminum and dialkylaluminum hydrides wherein the alkyl and alkoxy groups contain up to about 6 carbon atoms. Other examples are Grignard reagents, allyl and alkyl tin complexes, and the like. The reducing agent must be compatible with the Lewis acid and be capable of reducing zirconium acetylacetonate, preferably to an oxidation state lower than 4 and even to 0.

Where the reducing agent does not also function as a Lewis acid, an additional Lewis acid component can be supplied by a compound which is other than a protonic or hydrogen acid and which is capable of receiving one or more pairs of electrons to form a coordination bond. Lewis acids are well known to the art and are fully defined for example by Noller Chemistry of Organic Compounds, W. B. Saunders, 1951, at pages 233-235, by Stone Chemical Review (1958) at page 101, and by G. N. Lewis, Journal of the Franklin Institute (1938), pages 226-293. Examples of Lewis acids which are not included as a component ofa compound which also serves as a reducing agent include borontrifluoride, boron-trifluoride etherates, e.g., diethyleth crate, aluminum trihalides, zinc halides and stannic halides.

The preparation of the overall catalyst composition is preferably conducted by first forming the complex of the electron donor ligand and the zirconium source and then adding to a solution or suspension of that complex, in a suitable organic solvent, the reducing agent and the Lewis acid. Suitable organic solvents for the final catalyst composition are those which are inert to the catalyst and which will not significantly enter into, or deleteriously affect, the eventual polymerization reaction. As specific examples thereof may be mentioned aromatic and aliphatic hydrocarbons and their halogenated, e.g., chlorinated, derivatives. Oxygen-containing solvents are generally to be avoided for this purpose.

Formation of the ligand-zirconium complex may be effected by simply mixing the two reactants in the presence of a suitable solvent for the complexing reaction. The mixing may be done at room temperature or at temperatures as high as about 300F. The complex usu' ally forms within about to 40 minutes after mixing at elevated temperatures. Suitable solvents for the complex-forming reaction include the same solvents which are suitable for use in the final catalyst composition. A mixture of solvents may also be employed. For example, the ligand-zirconium complex may be formed in chlorobenzene and the Lewis acid-reducing agent added in the form of a solution in toluene. If desired,

the complexing may be accomplished in a solvent which is unsuitable for use in the final composition; in this case the resultant complex will first be isolated from the reaction mixture and redissolved, or resuspended, in a proper solvent which is inert to the final catalyst composition.

Thus, for example, one method of preparing a phosphinezirconium complex can involve stirring, preferably at room temperature, a mixture of triphenylphosphine, zirconium acetylacetonate and chlorobenzene. After the resulting complex has been formed, ethylaluminum sesquichloride in toluene may then be added directly to the reactant mixture.

The addition to the complex solution of the reducing agent and Lewis acid is preferably conducted in a dry, inert atmosphere, out of the presence of air, for instance in an autoclave. Within a relatively short period of time after the admixing of the components, e.g., about 5 to 15 minutes, an active catalyst composition is formed which may be used to catalyze the polymerization of low molecular weight olefins.

The catalyst compositions of this invention may be used to catalyze the production of liquid polymers, including dimers and oligomers, of mono-ethylenically unsaturated olefinic hydrocarbons of 2 to about 6, or even up to about 8, carbon atoms, as well as monophenyl-or-diphenyl derivatives thereof. By the terms polymerization and polymer it is meant to include herein copolymerization and copolymers as well as homopolymerization and homopolymers, and oligomerization and oligomers, e.g., dimerization and dimers, trimerization and trimers, etc., as well as crossor co-oligomerization e.g., crossor co-dimerization, etc. For example, by cross-dimerization, used here as being synonymous with codimerization, is meant the addition reaction combining one mole of a first olefin, for instance propylene, with one mole of a second olefin, for instance, butene, to form one mole of a crossdimer, for instance heptene. By dimerization, on the other hand, is meant the addition reaction which simply combines two moles of a single olefin, for instance propylene, to form the respective dimer, for instance hexene. Polymerization and polymers are the terms here used to embrace all of these reactions and reaction products.

Thus, suitable feeds include, for instance, monoethylenically unsaturated olefins, such as internaland a1- pha-olefins, such as ethylene, propylene and butenes; and phenyl-substituted derivatives of the foregoing olefins, such as styrene and l-phenylbutene-2. The polymers produced by the action of this present catalyst composition will often be of 2 to about 4 monomer units per molecule, i.e., will often range from dimers to tetramers. The catalyst composition has been found, for example, to be especially suitable for the production of hexene fractions by the dimerization of propylene.

Polymerization can be effected by contacting the olefinically-unsaturated feed at an elevated temperature of, for instance, about to 300F., preferably about to F., which can be maintained by an external heating means. A pressure of about 0 to 600 or more psig, preferably about 250 to 600 psig, is suitable with the catalyst composition of the present invention. Generally, higher pressures and temperatures are favorable for the reaction. The amount of catalyst composition used in the reaction is that sufficient to effect EXAMPLE n A subsequent set of reactions was run in the manner as in Example 1, but tri-n-butylphosphine was substituted for triphenylphosphine. The amounts of the components were the same as the amounts employed in Example l. The reaction conditions, catalyst composition and products of the reactions are listed in Tables 1 and 11.

TABLE 1 Catalyst Composition and Reaction Conditions Catalyst Composition Reaction Conditions Example Run Feed Zr(acac) R 1 R in Et Al- Cl Solvent Pressure Temp. Time No. No. C g m mole m mole R P m mole g. psig F. Hrs.

A 125 2.0 10.0 25 33 150450 155 A l B 135 2.0 10.0 d) 25 33 300-600 150 l-A C 135 2.0 10.0 (b 25 33 150-280 155 1% A 131 2.0 10.0 n-Bu 25 38 80-600 150 1 /2 11 B 137 2.0 10.0 n-Bu 25 38 130-600 153 l% Note: A mixture of chlorobenzene and toluene.

TABLE 11 Distribution of Products Example No. 1A 1B 1C 11A 11B C omponent" Weight /r 4-MC 3-MC P, 2.32 3.36 4.37 2.38 5.01 4-MC 8.98 11.20 13.77 8.70 15.84 2,3-DMCF'. 4-MC 31.35 28.71 29.85 46.70 56.82 Cf. 2MC,-, 14.67 13.34 13.61 12.46 9.69 Cf 4.01 3.04 2.66 1.96 1.03 2MC 13.34 11.82 10.90 6.32 3.38 C.; 3-MCf 17.10 17.13 16.43 15.32 7.41 4,4DMC 4.23 4.41 4.28 1.91 0.83 CFC 2.25 5.48 0.51 2.14 Yield. "/1 65.3 62.2 66.7 69.0 64.0

Note:

4-MCf is 4-methylpemcne-l; 4.4-DMCJ is 4.4-dimeth lpcntene 2 (trans); ete.

EXAMPLE I A stainless steel autoclave was used as a reactor. Zirconium acetylacetonate in the amount of 2.0 m. moles (millimoles) and triphenylphosphine in the amount of 10.0 m. moles were weighed into the reactor together with ml. of chlorobenzene. The reactor was purged thoroughly with nitrogen and the contents were stirred vigorously for 15 minutes. Ethylaluminum sesquichloride (Et Al Clin the amount of m. moles was then added through a septum in the form of a 25 percent solution in toluene. A small amount of toluene (5ml.) was used to wash the Et Al Cl through the delivery line into the reactor. After heating the contents to 125F.

for 15 minutes, 240 ml. of propylene was introduced into the reactor. The temperature of the contents was adjusted to 155F. A rapid pressure drop (approximately 10 psig/min.) persisted for 45 minutes. The reaction was terminated by cooling the contents to 90F.

' peated. The results of this recharge and one additional recharge are listed in Table 11.

I (is It is claimed:

1. In a process for polymerizing propylene to dimers through tetramers, the improvement which comprises conducting said polymerization in contact with a catalyst comprising a complex of A. zirconium acetylacetonate;

B. an electron donor ligand phosphine of the formula R P wherein each R is a hydrocarbon of up to 20 carbon atoms selected from the group consisting of alkyl, aryl, alkaryl, aralkyl and cycloalkyl, with C. a combination of a reducing agent capable of reducing zirconium acetylacetonate to an oxidation state of less than 4 and a non-protonic Lewis acid capable of forming a coordination bond with zirconium selected from a compound represented by the formula wherein R is alkyl of 2 to about 6 carbon atoms, X is chlorine, M is a metallic element of coordination number n whose halides are Lewis acids selected from aluminum, magnesium, beryllium, lead. zinc and tin and y is a number having a value o1- ll'om greater than 0 to n; the molar ratio of (B) to (A) being about 2 to 7:1 and the molar ratio of (C) to (A) being about 10 to 20:1, said components (C) and (A) being combined to reduce zirconium represented by (A) to an oxidation state of less than 4, and form a coordination bond with (A), and recovery of a polymerized propylene hydrocarbon product containing at least one dimer through tetramer.

2. ln a process for polymerizing propylene to dimers through tetramers, the improvement which comprises conducting said polymerization in contact with a catalyst comprising a complex of A. zirconium acetylacetonate;

B. an electron donor ligand phosphine of the formula wherein R is a hydrocarbon of up to carbon atoms, with C. a combination of a reducing agent capable of reducing zirconium acetylacetonate to an oxidation state of less than 4 and a non-protonic Lewis acid capable of forming a coordination bond with zirconium selected from a compound represented by the formula wherein R is alkyl of 2 to about 6 carbon atoms, X is chlorine, M is aluminum and y is a number having a value from greater than 0 to n and n is a coordination number of aluminum; the molar ratio of (B) to (A) being about 2 to 7:1 and the molar ratio of (C) to (A) being about 10 to 20:1, said components (C) and (A) being combined to reduce zirconium represented by (A) to an oxidation state of less than 4, and form a co ordination bond with (A), and recovery of a polymerized propylene hydrocarbon product containing at least one dimer through tetramer. 

1. IN A PROCESS FOR POLYMERIZING PROPYLENE TO DIMERS THROUGH TETRAMERS, THE IMPROVEMENT WHICH COMPRISES CONDUCTING SAID POLYMERIZATION IN CONTACT WITH A CATALYST COMPRISING A COMPLEX OF A. ZIRCONIUM ACETYLACETONATE; B. AN ELECTRON DONOR LIGAND PHOSPHINE OF THE FORMULA R3P WHEREIN EACH R IS A HYDROCARBON OF UP TO 20 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL, ALKARYL, ARALKYL AND CYCLOALKYL, WITH C. A COMBINATION OF A REDUCING AGENT CAPABLE OF REDUCING ZIRCONIUM ACETYLACETONATE TO AN OXIDATION STATE OF LESS THAN 4 AND A NON-PROTONIC LEWIS ACID CAPABLE OF FORMING A COORDINATION BOND WITH ZIRCONIUM SELECTED FROM A COMPOUND REPRESENTED BY THE FORMULA
 2. In a process for polymerizing propylene to dimers through tetramers, the improvement which comprises conducting said polymerization in contact with a catalyst comprising a complex of A. zirconium acetylacetonate; B. an electron donor ligand phosphine of the formula R3P wherein R is a hydrocarbon of up to 20 carbon atoms, with C. a combination of a reducing agent capable of reducing zirconium acetylacetonate to an oxidation state of less than 4 and a non-protonic Lewis acid capable of forming a coordination bond with zirconium selected from a compound represented by the formula R''(n y)MXy wherein R'' is alkyl of 2 to about 6 carbon atoms, X is chlorine, M is aluminum and y is a number having a value from greater than 0 to n'' and n'' is a coordination number of aluminum; the molar ratio of (B) to (A) being about 2 to 7:1 and the molar ratio of (C) to (A) being about 10 to 20:1, said components (C) and (A) being combined to reduce zirconium represented by (A) to an oxidation state of less than 4, and form a coordination bond with (A), and recovery of a polymerized propylene hydrocarbon product containing at least one dimer through tetramer. 